Solid pigment preparations containing pigment derivatives and surface-active additives

ABSTRACT

Solid pigment preparations containing the following ingredients as substantial components: (A) 60-85 wt. % of at least one organic pigment, (B) 0.1-15 wt. % of at least one pigment derivative of general formula I wherein the variables have the following meanings: P is the radical of the parent substance of an organic pigment; T 1 , T 2  independently represent a chemical bond, —CONR 1 — or —SO 2 NR 1 —; B 1 , B 2  independently represent a chemical bond, C1-C8-alkylene or phenylene;X, Y independently represent similar or different groups —SO 3 — Ka +  or —COO— Ka + ; m, n represent a rational number from 0 to 3, whereby 1=m+n=4; Ka +  H + , Li + , Na + , K + , N + R 2 R 3  R 4  R 5  or a mixture of said cations; R 1  represents hydrogen; C 1 -C 4 -alkyl; phenyl or naphthyl which can be respectively substituted by C 1 -C 18 -alkyl; R 2 , R 3 , R 4 , R 5  independently represent hydrogen; C 1 -C 30 -alkyl; C 3 -C 30 -alkenyl; C 5 -C 6 -cycloalkyl which can be substituted by C 1 -C 24 -alkyl; phenyl or naphthyl which can be respectively substituted by C 1 -C 24 -alkyl or C 2 -C 24 -alkenyl; a radical of formula —[CHR 6 —CHR 7 —O]x—R 8 , wherein the repeating units —[CHR 6 —CHR 7 —O] for x&gt; 1  can vary; R 6 , R 7 , R 8  independently represent hydrogen or C 1 -C 6 -alkyl; x is a whole number= 1 , and (C) 14.9 39.9 wt. % of at least one surface active additive from the group of non-ionic polyethers containing no primary amino groups, the acidic phosphoric acid esters,phosphonic acid esters, sulphuric acid esters and/or sulfonic acid esters thereof, the salts thereof and the condensation produces thereof with formaldehyde.

The present invention relates to solid pigment preparations comprisingas essential constituents

-   (A) from 60% to 85% by weight of at least one organic pigment,-   (B) from 0.1% to 15% by weight of at least one pigment derivative of    the general formula I    where    -   P is the residue of the core structure of an organic pigment;    -   T¹ and T² are independently a chemical bond, —CONR¹ — or        —SO₂NR¹—;    -   B¹ and B² are independently a chemical bond, C₁-C₈-alkylene or        phenylene;    -   X and Y independently represent identical or different groups        —SO₃ ⁻Ka⁺ or —COO⁻Ka⁺;    -   m and n are each a rational number from 0 to 3 subject to the        proviso that 1≦m+n≦4;    -   Ka⁺ is H⁺, Li⁺, Na⁺, K⁺, N⁺R²R³R⁴R⁵ or a mixture thereof;    -   R¹ is hydrogen; C₁-C₄-alkyl; unsubstituted or        C₁-C₁₈-alkyl-substituted phenyl; or unsubstituted or        C₁-C₁₈alkyl-substituted naphthyl;    -   R², R³, R⁴ and R⁵ are independently hydrogen; C₁-C₃₀-alkyl;        C₃-C₃₀-alkenyl; C₅-C₆-cycloalkyl, unsubstituted or        C₁-C₂₄-alkyl-substituted; unsubstituted or C₁-C₂₄-alkyl— or        C₂-C₂₄-alkenyl-substituted phenyl; unsubstituted or        C₁-C₂₄-alkyl— or C₂-C₂₄-alkenyl-substituted naphthyl; a radical        of the formula −[CHR⁶—CHR⁷—O]_(x)—R⁸ where the repeat units        −[CHR⁶—CHR⁷—O] can vary for x>1;    -   R⁶, R⁷and R⁸ are independently hydrogen or C₁-C₆-alkyl;    -   x is an integer ≧1, and-   (C) from 14.9% by weight to 39.9% by weight of at least one    surface-active additive selected from the group consisting of the    nonionic polyethers comprising no primary amino group, said    polyethers' acidic phosphoric, phosphonic, sulfuric and/or sulfonic    esters, the salts of these esters and the alkyl- and    alkylarylsulfonic acids, their salts and their condensation products    with formaldehyde.

The present invention further relates to the production of these pigmentpreparations and their use for coloration of macromolecular organic andinorganic materials and also of plastics.

Liquid systems such as coatings, varnishes, emulsion paints and printinginks are customarily pigmented using pigment formulations which comprisewater, organic solvent or mixtures thereof. As well as anionic,cationic, nonionic and amphoteric dispersants, these pigmentformulations generally have to be additized with further assistants,such as dried-crust inhibitors, freeze resistance enhancers, thickenersand anti-skinners, for stabilization.

There is a need for novel pigment preparations which are comparable toliquid formulations with regard to color properties and dispersibility,but do not require the additions mentioned and are easier to handle.However, simply drying liquid formulations does not provide solidpigment preparations having comparable performance properties.

The coloration of plastics requires complete dispersion of the pigmentin the plastic for the development of maximum color strength and coloreffect. For the pulverulent pigments typically used such dispersionrequires appropriate know-how and a high input of shearing energy andtherefore is costly. When the plastics processor does not possess thisknow-how and the requisite complicated and costly dispersion equipment,the colored plastics will often contain specks of incompletely dispersedpigment agglomerates, be difficult to spin and/or possess highpressure-filter values. Many plastics processors therefore employmasterbatches. A masterbatch is a typically solid, concentrated pigmentformulation in a plastics matrix which is solid at room temperature andmeltable and in which the pulverulent pigment is present in a state ofcomplete dispersion and hence in a fine state of subdivision; that is,the energy needed to disperse the pulverulent pigment has already beeninvested to produce the masterbatch.

A number of solid pigment preparations are known which are based oncopper phthalocyanine (CuPc) pigments in particular and which comprise aderivative of the pigment as well as the pigment itself. However, theydiffer in the rest of their composition from the pigment preparations ofthe present invention.

For instance, the CuPc pigment preparations described in WO-A-02/40596and JP-A-323 166/1999 do not comprise nonionic surface-active additivein the free state, ie not a salt of the CuPc pigment derivative, noradditional anionic surface-active additive.

The CuPc pigment preparations known from DE-A-42 14 868 andWO-A-02/48268 (or indeed the diketopyrrolopyrrole and indanthronepigment preparations disclosed therein) do not comprise nonionic oranionic surfactants, but only cationic surfactants which have beenreacted with the pigment derivative.

The CuPc pigment preparations of EP-A-621 319 include an inorganic ororganic salt as an essential constituent and no surfactants.

U.S. Pat. No. 4,726,847 describes CuPc pigment preparations where theCuPc pigment derivative and the comprised anionic surfactant are lakedto form the barium salt.

EP-A-761 770 discloses CuPc pigment preparations which comprise onlycationic surfactants in addition to aluminum resinates as essentialconstituents.

WO-A-02/64680 discloses preparations of various organic pigments, butthese do not comprise any surfactants. This also applies to thedioxazine and perylene pigment preparations which are disclosed inEP-A-504 922 and DE-A-39 26 564 respectively.

EP-A-636 666 and DE-A-43 21 693 describe perylene and indanthronepigment preparations which comprise respectively a perylene ordiaminoanthraquinone derivative as a pigment derivative and also anonionic surface-active additive. However, the total amount of additiveused is distinctly lower than in the case of the pigment preparations ofthe present invention.

These known pigment preparations all have the disadvantage of lackingsimple stir-in dispersibility in liquid application media.

DE-A-102 27 657, 102 28 199 and 102 33 081, each unpublished at thepriority date of the present invention, describe solid pigmentpreparations in granule form which comprise nonionic and/or anionicsurfactants but no pigment derivatives.

It is an object of the present invention to provide solid pigmentpreparations having altogether advantageous performance properties,especially high color strength and particularly good dispersibility in awide variety of application media, especially stir-in characteristics inliquid application media.

We have found that this object is achieved by solid pigment preparationscomprising as essential constituents

-   (A) from 60% to 85% by weight of at least one organic pigment,-   (B) from 0.1 % to 15% by weight of at least one pigment derivative    of the general formula I    where    -   P is the residue of the core structure of an organic pigment;    -   T¹ and T² are independently a chemical bond, —CONR¹ — or        —SO₂NR¹—;    -   B¹ and B² are independently a chemical bond, C₁-C₈-alkylene or        phenylene;    -   X and Y independently represent identical or different groups        —SO₃ ⁻Ka⁺ or —COO⁻Ka⁺;    -   m and n are each a rational number from 0 to 3 subject to the        proviso that 1≦m+n≦4;    -   Ka⁺ is H⁺, Li⁺, Na⁺, K⁺, N⁺R²R³R⁴R⁵ or a mixture thereof;    -   R¹ is hydrogen; C₁-C₄-alkyl; unsubstituted or        C₁-C₁₈-alkyl-substituted phenyl; or unsubstituted or        C₁-C₁₈alkyl-substituted naphthyl;    -   R², R³, R⁴ and R⁵ are independently hydrogen; C₁-C₃₀-alkyl;        C₃-C₃₀-alkenyl; C₅-C₆-cycloalkyl, unsubstituted or        C₁-C₂₄-alkyl-substituted; unsubstituted or C₁-C₂₄-alkyl— or        C₂-C₂₄-alkenyl-substituted phenyl; unsubstituted or        C₁-C₂₄-alkyl— or C₂-C₂₄-alkenyl-substituted naphthyl; a radical        of the formula −[CHR⁶—CHR⁷—O]_(x)—R⁸ where the repeat units        −[CHR⁶—CHR⁷—O] can vary for x>1;    -   R⁶, R⁷and R⁸ are independently hydrogen or C₁-C₆-alkyl;    -   x is an integer ≧1, and-   (C) from 14.9% by weight to 39.9% by weight of at least one    surfaceactive additive selected from the group consisting of the    nonionic polyethers comprising no primary amino group, said    polyethers' acidic phosphoric, phosphonic, sulfuric and/or sulfonic    esters, the salts of these esters and the alkyl- and    alkylarylsulfonic acids, their salts and their condensation products    with formaldehyde.

The present invention further provides a process for producing thepigment preparations, which comprises wet-comminuting the pigment (A) inaqueous suspension which comprises some or all of additive (C) and, ifdesired, some or all of pigment derivative (B) and also, if desired,prior or subsequent neutralization of the suspension with a base andthen drying the suspension, if necessary after the rest of pigmentderivative (B) and additive (C) has been added.

The present invention further provides a process for coloration ofmacromolecular organic and inorganic materials, which comprisesincorporating the pigment preparations in these materials by stirring orshaking.

The present invention lastly provides a process for coloration ofplastics, which comprises incorporating the pigment preparations in theplastics by extruding, rolling, kneading or milling.

The pigment preparations of the present invention comprise as essentialconstituents a pigment (A), a pigment derivative (B) and a water-solublesurface-active additive (C).

Component (A) in the pigment preparations of the present invention is atleast one organic pigment. It will be appreciated that the pigmentpreparations of the present invention may also comprise mixtures ofvarious organic pigments. In principle it is also possible for mixturesof organic pigments with inorganic pigments, especially with inorganicwhite pigments or fillers, to be comprised.

The pigments (A) are present in a finely divided form. Their averageparticle size is accordingly in general in the range from 0.01 to 5 μmand especially in the range from 0.05 to 3 μm.

The organic pigments are typically organic chromatic and black pigments.Inorganic pigments can likewise be color pigments (chromatic, black andwhite pigments) and also luster pigments and the inorganic pigmentstypically used as fillers.

There now follow examples of suitable organic color pigments:

-   -   monoazo pigments: C.I. Pigment Brown 25;        -   C.I. Pigment Orange 5,13, 36, 38, 64 and 67;        -   C.I. Pigment Red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31,            48:1, 48:2, 48:3, 48:4, 49, 49:1, 51:1, 52:1, 52:2, 53,            53:1, 53:3, 57:1, 58:2, 58:4, 63, 112, 146, 148, 170, 175,            184, 185, 187, 191:1, 208, 210, 245, 247 and 251;        -   C.I. Pigment Yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154,            168, 181, 183 and 191;        -   C.I. Pigment Violet 32;    -   disazo pigments: C.I. Pigment Orange 16, 34, 44 and 72;        -   C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113,            126, 127, 155, 174, 176, 180 and 188;    -   disazo condensation pigments: C.I. Pigment Yellow 93, 95 and        128;        -   C.I. Pigment Red 144, 166, 214, 220, 221, 242 and 262;        -   C.I. Pigment Brown 23 and 41;    -   anthanthrone pigments: C.I. Pigment Red 168;    -   anthraquinone pigments: C.I. Pigment Yellow 147, 177 and 199;        -   C.I. Pigment Violet 31;    -   anthrapyrimidine pigments: C.I. Pigment Yellow 108;    -   quinacridone pigments: C.I. Pigment Orange 48 and 49;        -   C.I. Pigment Red 122, 202, 206 and 209;        -   C.I. Pigment Violet 19;    -   quinophthalone pigments: C.I. Pigment Yellow 138;    -   diketopyrrolopyrrole pigments: C.I. Pigment Orange 71, 73 and        81;        -   C.I. Pigment Red 254, 255, 264, 270 and 272;    -   dioxazine pigments: C.I. Pigment Violet 23 and 37;        -   C.I. Pigment Blue 80;    -   flavanthrone pigments: C.I. Pigment Yellow 24;    -   indanthrone pigments: C.I. Pigment Blue 60 and 64;    -   isoindoline pigments: C.I. Pigment Orange 61 and 69;        -   C.I. Pigment Red 260;        -   C.I. Pigment Yellow 139 and 185;    -   isoindolinone pigments: C.I. Pigment Yellow 109, 110 and 173;    -   isoviolanthrone pigments: C.I. Pigment Violet 31;    -   metal complex pigments: C.I. Pigment Red 257;        -   C.I. Pigment Yellow 117, 129, 150, 153 and 177;        -   C.I. Pigment Green 8;    -   perinone pigments: C.I. Pigment Orange 43;        -   C.I. Pigment Red 194;    -   peryiene pigments: C.I. Pigment Black 31 and 32;        -   C.I. Pigment Red 123, 149, 178, 179, 190 and 224;        -   C.I. Pigment Violet 29;    -   phthalocyanine pigments: C.I. Pigment Blue 15, 15:1, 15:2, 15:3,        15:4, 15:6 and 16;        -   C.I. Pigment Green 7 and 36;    -   pyranthrone pigments: C.I. Pigment Orange 51;        -   C.I. Pigment Red 216;    -   pyrazoloquinazolone pigments: C.I. Pigment Orange 67;        -   C.I. Pigment Red 251;    -   thioindigo pigments: C.I. Pigment Red 88 and 181;        -   C.I. Pigment Violet 38;    -   triarylcarbonium pigments: C.I. Pigment Blue 1, 61 and 62;        -   C.I. Pigment Green 1;        -   C.I. Pigment Red 81, 81:1 and 169;        -   C.I. Pigment Violet 1, 2, 3 and 27;    -   C.I. Pigment Black 1 (aniline black);    -   C.I. Pigment Yellow 101 (aldazine yellow);    -   C.I. Pigment Brown 22.

Examples of suitable inorganic color pigments are:

-   -   white pigments: titanium dioxide (C.I. Pigment White 6), zinc        white, pigment grade zinc oxide; zinc sulfide, lithopone;    -   black pigments: iron oxide black (C.I. Pigment Black), iron        manganese black (C.I. Pigment Black 27); carbon black (C.I.        Pigment Black 7);    -   chromatic pigments: chromium oxide, chromium oxide hydrate        green; chrome green (C.I. Pigment Green 48); cobalt green (C.I.        Pigment Green 50); ultramarine green;        -   cobalt blue (C.I. Pigment Blue 28 and36; C.I. Pigment Blue            72); ultramarine blue; manganese blue,        -   ultramarine violet; cobalt violet and manganese violet;        -   red iron oxide (C.I. Pigment Red 101); cadmium sulfoselenide            (C.I. Pigment Red 108); cerium sulfide (C.I. Pigment Red            265); molybdate red (C.I. Pigment Red 104); ultramarine red;        -   brown iron oxide (C.I. Pigment Brown 6 and 7), mixed brown,            spinel phases and corundum phases (C.I. Pigment Brown 29,            31, 33, 34, 35, 37, 39 and 40), chromium titanium yellow            (C.I. Pigment Brown 24), chrome orange;        -   cerium sulfide (C.I. Pigment Orange 75);        -   yellow iron oxide (C.I. Pigment Yellow 42); nickel titanium            yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157,            158, 159, 160, 161, 162, 163, 164 and 189); chromium            titanium yellow; spinel phases (C.I. Pigment Yellow 119);            cadmium sulfide and cadmium zinc sulfide (C.I. Pigment            Yellow 37 and 35); chrome yellow (C.I. Pigment Yellow 34);            bismuth vanadate (C.I. Pigment Yellow 184).

Examples of inorganic pigments typically used as fillers are transparentsilicon dioxide, ground quartz, aluminum oxide, aluminum hydroxide,natural micas, natural and precipitated chalk and barium sulfate.

Luster pigments are platelet-shaped pigments having a monophasic orpolyphasic construction whose color play is marked by the interplay ofinterference, reflection and absorption phenomena. Examples are aluminumplatelets and aluminum, iron oxide and mica platelets bearing one ormore coats, especially of metal oxides.

The pigment preparations of the present invention comprise from 60% to85% by weight and preferably from 70% to 85% by weight of pigment (A).

Component (B) in the solid pigment preparations of the present inventionis a pigment derivative of the above-defined formula I

The pigment derivatives I are based on an organic pigment's corestructure P which is functionalized by a sulfonic acid and/or carboxylicacid groups which are attached to the core structure either directly orvia bridging elements. The term “core structure” as used herein shallcomprehend the pigments themselves and also their precursors. Pigmentprecursors come into consideration in the case of polycyclic pigments inparticular. They have the ring structure of the pigment, but thepigment's full substitution pattern is not present and/orfunctionalizations are missing. Perylene-3,4-dicarboximides may bementioned as an example of a precursor to perylene pigments based onperylene-3,4,9,10-tetracarboxylic acids and their diimides.

The pigment derivative I used as a component (B) in a particular pigmentpreparation can have the same pigment core structure P as the organicpigment (A). The scope for possible combinations is limited by therequirement that the colored pigment derivative (B) should not adverselyaffect the color due to pigment (A) in the application medium.

In principle, the core structures of pigments selected from the groupconsisting of the anthraquinone, quinacridone, quinophthalone,diketopyrrolopyrrole, dioxazine, flavanthrone, indanthrone, isoindoline,isoindolinone, isoviolanthrone, perinone, perylene, phthalocyanine,pyranthrone, pyrazoloquinazolone and thioindigo pigments are preferredfor the pigment derivatives I. Owing to their broad utility, pigmentcore structures selected from the group consisting of thequinophthalone, perylene and phthalocyanine pigments are particularlypreferred. Among these, it is in turn the pigment core structuresselected from the group consisting of the quinophthalone andphthalocyanine pigments which are most preferred. Quinophthalone-basedpigment derivatives I (especially the hereinbelow more particularlydescribed pigment derivative Ia) are particularly useful for combinationwith yellow, orange and red pigments, while phthalocyanine-based pigmentderivatives I (in particular the hereinbelow likewise more particularlydescribed pigment derivative Ib) are especially useful for combinationwith blue, green, violet and black pigments.

Preferably, the sulfonic acid and/or carboxylic acid groups X and Y aredirectly attached to the pigment core structure P in the pigmentderivatives I, ie T¹ and B¹ and also T² and B² are all preferably achemical bond.

However, T¹ and T² may also be bridging moieties of the formula —CONR¹—or —SO₂NR¹— (R¹: hydrogen; C₁-C₄-alkyl; naphthyl or especially phenyl,which may each be substituted by C₁-C₁₈-alkyl but each preferablyunsubstituted). Examples of particularly useful bridging moieties T¹ andT² are —CONH—, SO₂NH—, —CON(CH₃)— and —SO₂N(CH₃)—.

Similarly, B¹ and B² may be branched or unbranched C₁-C₈-alkyleneradicals or phenylene radicals. Examples are: methylene, 1,1- and1,2-ethylene, 1,1-, 1,2- and 1,3-propylene and 1,4-, 1,3- and1,2-phenylene.

Examples of suitable combinations of the bridging moieties T and B are—CONH—CH₂—, —CON(CH₃)—CH₂—, —CONH—C₂H₄—, —CONH—CH(CH₃)—, —SO₂NH—CH₂—,—SO₂N(CH₃)—CH₂—, —SO₂NH—C₂H₄—, —SO₂NH—CH(CH₃)—, —CONH-1,4-C₆H₄— and—SO₂NH-1,4-C₆H₄—.

The sulfonic acid and/or carboxylic acid groups X and Y may each bepresent as a free acid or as a salt (Ka⁺: Li⁺, Na⁺, K⁺ or N⁺R²R³R⁴R⁵).

The ammonium salts may be formed of unsubstituted ammonium ions, butpreferably at least one of R², R³, R⁴ and R⁵ is other than hydrogen.

Suitable aliphatic radicals R², R³, R⁴ and R⁵ are C₁-C₃₀-alkyl andC₃-C₃₀-alkenyl radicals which may each be branched or unbranched andC₅-C₆-cycloalkyl radicals which may be substituted by C₁-C₂₄-alkyl andpreferably by C₁-C₁₈-alkyl. Useful aromatic radicals are phenyl andnaphthyl which may each be substituted by C₁-C₂₄-alkyl or byC₂-C₂₄-alkenyl, especially by C₁-C₁₈-alkyl or C₂-C₁₈-alkenyl. Theradicals R², R³, R⁴ and R⁵ may also be polyalkyleneoxy radicals of theformula —[CHR⁶—CHR⁷—O]_(x)—R⁸ (R⁶, R⁷ and R⁸: independently hydrogen,C₁-C₆-alkyl; x≧1). When x is>1, the radicals can be homopolymeric, iefor example pure polyethyleneoxy or pure polypropyleneoxy radicals, orcopolymeric radicals which contain the various alkyleneoxy unitsespecially as blocks or else randomly, for examplepolyethyleneoxy-polypropyleneoxy radicals.

Preference is given to aromatic and particular preference to noncyclicaliphatic radicals R², R³, R⁴ and R⁵.

Most particularly suitable ammonium salts are mono-C₈-C₃₀-alkyl- or-alkenylammonium salts, eg lauryl, stearyl, oleyl or tallowalkylammonium salts, and also quatemized ammonium salts which comprisefrom 24 to 42 carbon atoms in total, provided at least one andpreferably two of the alkyl and/or alkenyl radicals have at least 8,preferably 12 and more preferably from 12 to 20 carbon atoms, egdimethyididodecyl-, dimethyidioleyl- and dimethyldistearylammoniumsalts.

Preferably, the sulfonic acid and/or carboxylic acid groups X and Y arenot present in free form in the pigment derivatives I. When they havenot already been converted to the salt, the formation of the salt andespecially the formation of the sodium salt generally takes place in thecourse of the production of the pigment preparations for the presentinvention, which in this case preferably comprises a neutralizing step.When no or only incomplete salt formation has taken place and a nonionicsurface-active additive (C) is used that has a basic-site, for example anitrogen atom, the acid groups may of course also react with thisadditive to form a salt. However, even in this case the pigmentpreparations of the present invention still comprise free additive (C),preferably not less than 5% by weight of free additive (C). When theadditive (C) is incapable of salt formation, the sulfonic acid and/orcarboxylic acid groups may also be present as a free acid.

Mixtures of various salts will thus frequently be present. When this isthe case, the preferred sodium and/or ammonium salts (especially theammonium salts explicitly mentioned above) should at least constitute ahigh fraction of these mixtures.

The pigment derivatives I may comprise from 1 to 4 acid groups.Depending on the pigment core structure P, for example in the case of aphthalocyanine residue P, the pigment derivatives I can constituterandom mixtures of molecules having various degrees of substitution sothat the mean value of the sum m+n can be a fractional number.

Preferably, the pigment derivatives I comprise sulfonic acid groupsonly. In this case, a degree of substitution (m+n) in the range from 1to 3 and especially in the range from 1 to 2 will prove particularlyadvantageous. When the sulfonic acid groups are present in the form ofan ammonium salt (m) and optionally as sodium salt or as a free acid(n), then m is preferably in the range from 1 to 1.8 and n in the rangefrom 0 to 0.2.

Examples of particularly suitable pigment derivatives I are:

quinophthalonesulfonic acids of the formula Ia

copper phthalocyaninesulfonic acids of the formula Ib[CuPc]—(SO₃Ka⁺)_(m+n)  Ibperylenesulfonic acids of the formula Ic

Here, Ka⁺ and m+n have the meanings defined at the outset, although Kais preferably Na⁺ or N⁺R²R³R⁴R⁵ (especially with the above-recitedpreferred combinations of the radicals R² to R⁵). The sum m+n is inparticular 1 in the case of the compounds Ia and Ic, and the sulfonicacid group is preferably in position 6 in the case of the compounds Iaand preferably in position 9 in the case of the compounds Ic.

Rings A and A′ in the formula Ia may be the same or different and mayeach be substituted by from 1 to 4 chlorine and/or fluorine atoms.Preferably, each ring bears 4 chlorine atoms.

D represents —O— or —NR⁹—, where R⁹ is hydrogen, C₁-C₄-alkyl orunsubstituted or C₁-C₄-alkyl-substituted, C₁-C₄-alkoxy- and/orphenylazo-substituted phenyl. Preferably, R⁹ is hydrogen, methyl,4-ethoxyphenyl, 3,5-dimethylphenyl or 4-phenylazophenyl.

The components (B) which are most preferable are the pigment derivativesIa and Ib where the symbols each have the preferred meanings. In thisconnection, the pigment derivatives Ia are preferably in the form ofsodium salts and the pigment derivatives lb may be present not only assodium but also as ammonium salts.

The pigment derivatives I are known and can be prepared according toknown methods.

The pigment preparations of the present invention comprise from 0.1% to15% by weight and especially from 0.5% to 10% by weight of component(B). When component (B) is selected from the pigment derivatives Ia, itsfraction is preferably in the range from 0.1% to 5% by weight andespecially in the range from 0.5% to 4% by weight. In the case of thepigment derivatives Ib, amounts ranging from 2% to 10% by weight andespecially from 3% to 8% by weight are preferred. The level of pigmentderivatives Ic is preferably in the range from 0.1% to 5 weight-5 andespecially in the range from 0.5% to 3% by weight.

Component (C) in the pigment preparations of the present invention is atleast one surface-active additive. The surface-active additive may be anonionic additive based on polyethers which do not comprise any primaryamino groups or it may be an anionic additive based on acidicphosphoric, phosphonic, sulfuric and/or sulfonic esters of thesepolyethers and the salts of these esters and also on alkyl- andalkylarylsulfonic acids, their salts and their condensation productswith formaldehyde. It will be appreciated that it is also possible formixtures of various nonionic surface-active additives, mixtures ofvarious anionic surface-active additives or else mixtures of nonionicand anionic surface-active additives to be comprised in the pigmentpreparations of the present invention.

Water-soluble additives (C) are particularly useful in waterbomeapplication media in particular. Preference is here given to additives(C) which permit the preparation of at least 5% by weight and especiallyat least 10% by weight aqueous solutions.

The polyethers underlying the additives (C) are in particularpolyalkylene oxides, especially alkylene oxide block copolymers, orreaction products of alkylene oxides with alcohols, amines, aliphaticcarboxylic acids and carboxamides. For the purposes of the presentinvention, the term “alkylene oxide” as used herein shall alsocomprehend aryl-substituted alkylene oxide, especiallyphenyl-substituted ethylene oxide.

As well as unmixed polyalkylene oxides, preferably C₂-C₄-alkylene oxidesand phenyl-substituted C₂-C₄-alkylene oxides, especially polyethyleneoxides, polypropylene oxides and poly(phenylethylene oxide)s, it is inparticular block copolymers, especially polymers having polypropyleneoxide and polyethylene oxide blocks or poly(phenylethylene oxide) andpolyethylene oxide blocks, and also random copolymers of these alkyleneoxides which are suitable.

These polyalkylene oxides are preparable by polyaddition of alkyleneoxides onto initiator molecules, as onto saturated or unsaturatedaliphatic and aromatic alcohols, saturated or unsaturated aliphatic andaromatic amines, saturated or unsaturated aliphatic carboxylic acids andcarboxamides. It is customary to use from 1 to 300 mol and preferablyfrom 3 to 150 mol of alkylene oxide per mole of initiator molecule.

Suitable aliphatic alcohols comprise in general from 6 to 26 carbonatoms and preferably from 8 to 18 carbon atoms and can have anunbranched, branched or cyclic structure. Examples are octanol, nonanol,decanol, isodecanol, undecanol, dodecanol, 2-butyloctanol, tridecanol,isotridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol),2-hexyldecanol, heptadecanol, octadecanol (stearyl alcohol),2-heptylundecanol, 2-octyldecanol, 2-nonyltridecanol,2-decyltetradecanol, oleyl alcohol and 9-octadecenol and also mixturesof these alcohols, such as C₈/C₁₀, C₁₃/C₁₅ and C₁₆/C₁₈ alcohols, andcyclopentanol and cyclohexanol. Of particular interest are the saturatedor unsaturated fatty alcohols obtained from natural raw materials by fathydrolysis and reduction and the synthetic fatty alcohols from the oxoprocess. The alkylene oxide adducts with these alcohols typically haveaverage molecular weights M_(n) from 200 to 5,000.

Examples of the abovementioned aromatic alcohols indude not only α- andβ-naphthol and their C₁-C₄-alkyl derivatives but also in particularphenol and its C₁-C₁₂-alkyl derivatives, such as hexylphenol,heptylphenol, octylphenol, nonylphenol, isononylphenol, undecylphenol,dodecylphenol, di- and tributylphenol and dinonylphenol, and itsarylalkyl derivatives, especially its hydroxyphenylmethyl derivatives,the methyl group of which can be substituted by two C₁-C₈-alkyl radicalsbut preferably carries two methyl radicals (bisphenol A).

Suitable aliphatic amines correspond to the abovementioned aliphaticalcohols. Again of particular importance here are the saturated andunsaturated fatty amines which preferably have from 14 to 20 carbonatoms. Examples of suitable aromatic amines are aniline and itsderivatives.

Useful aliphatic carboxylic acids include especially saturated andunsaturated fatty acids which preferably comprise from 14 to 20 carbonatoms and fully hydrogenated, partially hydrogenated and unhydrogenatedresin acids and also polyfunctional carboxylic acids, for exampledicarboxylic acids, such as maleic acid.

Suitable carboxamides are derived from these carboxylic acids.

As well as alkylene oxide adducts with monofunctional amines andalcohols it is alkylene oxide adducts with at least bifunctional aminesand alcohols which are of very particular interest.

The at least bifunctional amines preferably have from 2 to 5 aminegroups and conform in particular to the formula H₂N—(R¹⁰—NR¹¹)p—H (R¹⁰:C₂-C₆-alkylene; R¹¹: hydrogen or C₁-C₆-alkyl; p: 1-5). Specific examplesare: ethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, 1,3-propylenediamine, dipropylenetriamine,3-amino-1-ethyleneamino-propane, hexamethylenediamine,dihexamethylenetriamine, 1,6-bis(3-aminopropylamino)hexane andN-methyidipropylenetriamine, of which hexamethylenediamine anddiethylenetriamine are more preferable and ethylenediamine is mostpreferable.

These amines are preferably reacted first with propylene oxide and thenwith ethylene oxide. The ethylene oxide content of the block copolymersis typically about 10% to 90% by weight.

The average molecular weights M_(n) of the block copolymers based onpolyamines are generally in the range from 1,000 to 40,000 andpreferably in the range from 1,500 to 30,000.

The at least bifunctional alcohols preferably have from two to fivehydroxyl groups. Examples are C₂-C₆-alkylene glycols and thecorresponding di- and polyalkylene glycols, such as ethylene glycol,1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol,1.,4butylene glycol, 1,6-hexylene glycol, dipropylene glycol andpolyethylene glycol, glycerol and pentaerythritol, of which ethyleneglycol and polyethylene glycol are more preferable and propylene glycoland dipropylene glycol are most preferable.

Particularly preferred alkylene oxide adducts with at least bifunctionalalcohols have a central polypropylene oxide block, ie are based on apropylene glycol or polypropylene glycol which is initially reacted withfurther propylene oxide and then with ethylene oxide. The ethylene oxidecontent of the block copolymers is typically in the range from 10% to90% by weight.

The average molecular weights M_(n) of the block copolymers based onpolyhydric alcohols are generally in the range from 1,000 to 20,000 andpreferably in the range from 1,000 to 15,000.

Such alkylene oxide block copolymers are known and commerciallyavailable for example under the names of Tetronic® and Pluronic® (BASF).

An important group of anionic surface-active additives (C) isconstituted by the phosphates, phosphonates, sulfates and sulfonates ofnonionic polyethers, of which phosphates and sulfates are preferred.

These are convertible by reaction with phosphoric acid, phosphoruspentoxide and phosphonic acid on the one hand or with sulfuric acid andsulfonic acid on the other into phosphonic mono- or diesters andphosphonic esters on the one hand and sulfuric monoesters and sulfonicesters on the other. These acidic esters are preferably present in theform of water-soluble salts, especially as alkali metal salts, inparticular sodium salts, and ammonium salts, but can also be used in theform of the free acids.

Preferred phosphates and phosphonates are derived in particular fromalkoxylated and especially ethoxylated fatty and oxo process alcohols,alkylphenols, fatty amines, fatty acids and resin acids, while preferredsulfates and sulfonates are based in particular on alkoxylated andespecially ethoxylated fatty alcohols, alkylphenols and amines,including polyfunctional amines.

A further important group of anionic surface-active additives (C) isthat constituted by aromatic sulfonates, such asp-C₈-C₂₀-alkylbenzenesulfonates, di-(C₁-C₈-alkyl)naphthalenesulfonatesand condensation products of naphthalenesulfonic acids withformaldehyde, and aliphatic sulfonates, such asC₁₂-C₁₈-alkanesulfonates, α-sulfo fatty acid C₂-C₈-alkyl esters,sulfosuccinic esters and alkoxy-, acyloxy- andacylaminoalkanesulfonates, which are preferably likewise used in theform of their water-soluble sodium salts.

Preference is here given to aryl sulfonates, anddi-(C₁-C₈-alkyl)naphthalenesulfonates are particularly preferred. Veryparticular preference is given to diisobutyl- anddiisopropyl-naphthalenesulfonate.

Such anionic surface-active additives are known and commerciallyavailable for example under the names of Crodafos® (Croda), Rhodafac®(Rhodia), Maphos® (BASF), Texapon® (Cognis), Empicol® (Albright &Wilson), Matexil® (ICI), Soprophor® (Rhodia), Lutensit® (BASF), Nekal®(BASF) and Tamol® (BASF).

The pigment preparations of the present invention comprise from 14.9% to34.9% by weight and preferably from 17% to 25% by weight of thesurface-active additive (C). As mentioned above, a nonionic additive (C)which has a basic site capable of salt formation may react withunneutralized pigment derivative (B) to form a salt. Care must be takenin this case to ensure that the pigment preparation still comprises freeadditive (nonionic and/or anionic additive (C)). Preferably, at least 5%by weight of additive (C) is present in free form.

The pigment preparations of the present invention may comprise nonionicadditive (C) alone, anionic additive (C) alone or mixtures of nonionicand anionic additive (C). For example, anionic additives based on thepreferred phosphoric and sulfuric esters of nonionic polyethers may beused in pure form or in mixtures with nonionic and/or further anionicadditives (C). The ester fraction of these mixtures may be in the rangefrom 5% to 90% by weight. Anionic additives (C) which are based on arylsulfonates are preferably used in mixture with nonionic and/or furtheranionic additives (C), in which case their fraction in the mixtures isgenerally in the range from 5% to 20% by weight.

The pigment preparations of the present invention are advantageouslyobtainable by the production process of the present invention bywet-comminuting the pigment (A) in an aqueous suspension which comprisessome but preferably all of additive (C) and then drying the suspension,if necessary after the rest of additive (C) has been added.

The pigment derivative (B) may be added to the suspension in thisproduction process before, during or after the wet-comminutingoperation, or even if desired in portions at various times. Preferably,at least some but preferably all of pigment derivative (B) is addedbefore the wet-comminuting operation. It is also possible to add thepigment derivative (B) to a suspension of the pigment (A), to filter offthe pigment coated with the pigment derivative (B) and to feed the moistpresscake, if desired after partial or full drying, to a wet-comminutingoperation.

The pigment (A) can be used in the process of the present invention as adry powder or in the form of a presscake. Preferably, the pigment (A) isused in the form of a finished product, ie the primary particle size ofthe pigment has already been adjusted to the desired application value.This finish, which may also be carried out in the presence of pigmentderivative (B), has to be carried out in the case of organic pigmentsespecially, since the as-synthesized crude material is not suitable foruse. Since the finished pigment (A) typically reagglomerates in thecourse of drying or on the filter assembly, it is subjected to wetcomminution, for example grinding in a stirred media mill, in aqueoussuspension.

The wet-comminuting operation can be carried out at various pH values.For drying, however, the suspension should have a pH of approximately 7,ie be neutralized. In general (and especially with the use of thepigment derivatives (B) in the form of the free acid) this will requirethe addition of a base, especially of aqueous sodium hydroxide solution,before or after the wet-comminuting operation. Preferably, however, thebase is added before the wet-comminuting operation.

The particle size of the pigment preparations of the present inventioncan be controlled to a specifically targeted value, depending on themethod which is chosen for drying—spray granulation and fluidized beddrying, spray drying, drying in a paddle dryer, evaporation andsubsequent comminution. The operation can be carried out not only in theair but also under inert gas, preferably nitrogen.

Spray and fluidized bed granulation may produce coarsely dividedgranules having average particle sizes from 50 to 5,000 μm andespecially from 100 to 1,000 μm. Spray drying typically producesgranules having average particle sizes <20 μm. Finely dividedpreparations are obtainable by drying in a paddle dryer and byevaporation with subsequent grinding. Preferably, however, the pigmentpreparations of the present invention are in granule form.

Spray granulation is preferably carried out in a spray tower using aone-material nozzle. Here, the suspension is sprayed in the form ofrelatively large drops, and the water evaporates. The additive (C) meltsat the drying temperatures and so leads to the formation of asubstantially spherical granule having a particularly smooth surface(BET values generally ≦15 m²/g, and especially ≦10 m²/g).

The gas inlet temperature in the spray tower is generally in the rangefrom 180 to 300° C. and preferably in the range from 150 to 300° C. Thegas outlet temperature is generally in the range from 70 to 150° C. andpreferably in the range from 70 to 130° C.

The residual moisture content of the granular pigment obtained ispreferably <2% by weight.

The pigment preparations of the present invention are notable in use fortheir excellent color properties which are comparable to those of liquidpigment formulations, especially with regard to color strength,brilliance, hue and hiding power, and in particular for their stir-incharacteristics, ie they can be dispersed in application media with aminimal input of energy, simply by stirring or shaking. This applies inparticular to the coarsely divided pigment granules, which constitutethe preferred embodiment of the pigment preparations of the presentinvention.

Compared with liquid pigment formulations, the pigment preparations ofthe present invention additionally have the following advantages: Theyhave a higher pigment content. Whereas liquid formulations tend tochange viscosity during storage and have to be admixed withpreservatives and agents for enhancing the resistance to freezing and/ordrying out (crusting), the pigment preparations of the present inventionexhibit very good stability in storage. They are both economically andecologically advantageous with regard to packaging, storage andtransportation. Since they are solvent free, they are more flexible inuse.

The pigment preparations of the present invention which are in granuleform are notable for excellent attrition resistance, a minimal tendencyto compact or clump, uniform particle size distribution, goodpourability, flowability and meterability and also dustlessness inhandling and application.

The pigment preparations of the present invention are very useful forpigmenting macromolecular organic and inorganic materials of any kind.Liquid application media in this context can also be purely aqueous;comprise mixtures of water and organic solvents, for example alcohols;or be based exclusively on organic solvents, such as alcohols, glycolethers, ketones, eg methyl ethyl ketone, amides, eg N-methylpyrrolidoneand dimethylformamide, esters, eg ethyl acetate, butyl acetate andmethoxypropyl acetate, or aromatic or aliphatic hydrocarbons, eg xylene,mineral oil and mineral spirits.

If desired, the preparations can initially be stirred into a solventwhich is compatible with the particular application medium, and thisstirring into the solvent is again possible with minimal input ofenergy, and then be introduced into this application medium. Forinstance, slurries of pigment preparations in glycols or other solventscustomary in the paint and coatings industry, such as methoxypropylacetate, can be used to render the pigment preparations adapted toaqueous systems compatible with hydrocarbonaceous systems or systemsbased on nitrocellulose.

Examples of materials which can be pigmented with the pigmentpreparations of the present invention include: coatings, for examplearchitectural coatings, industrial coatings, automotive coatings,radiation-curable coatings; paints, including paints for buildingexteriors and building interiors, for example wood paints, lime washes,distempers, emulsion paints; solventbome printing inks, for exampleoffset printing inks, flexographic printing inks, toluene gravureprinting inks, textile printing inks, radiation-curable printing inks;waterbome inks, including inkjet inks; color filters; building materials(water is typically added only after building material and granularpigment have been dry mixed), for example silicate render systems,cement, concrete, mortar, gypsum; bitumen, caulks; cellulosic materials,for example paper, paperboard, cardboard, wood and woodbase, which caneach be coated or otherwise finished; adhesives; film-forming polymericprotective colloids as used for example in the pharmaceutical industry,cosmetic articles; detergents.

The pigment preparations of the present invention are particularlyuseful as mixing components in color-mixing or -matching systems. Owingto their stir-in characteristics, they can be used directly as a solidfor this purpose. If desired, however, they can also be first convertedinto tinting colors (especially into colors having a high solidscontent, “HS colors”), or even more highly pigmented tinting pasteswhich then constitute the components of the mixing system. The matchingof the desired hue and hence the mixing of the color components can beeffected visually via a system of color cards in a very large number ofhue gradations which are based on color standards, such as RAL, BS andNCS, or preferably under computer control, whereby an unlimited numberof hues become accessible (“computer color matching”).

The pigment preparations are very useful for coloring plastics of allkinds. The following classes and types of plastics may be mentioned byway of example:

-   -   modified natural materials:    -   thermosets, eg casein plastics; thermoplastics, eg cellulose        nitrate, cellulose acetate, cellulose mixed esters and cellulose        ethers;    -   synthetic plastics:    -   polycondensates: thermosets, eg phenolic resin, urea resin,        thiourea resin, melamine resin, unsaturated polyester resin,        allylic resin, silicone, polyimide and polybenzimidazole;        thermoplastics, eg polyamide, polycarbonate, polyester,        polyphenylene oxide, polysulfone and polyvinyl acetal;    -   addition polymers: thermoplastics, eg polyolefins, such as        polyethylene, polypropylene, poly-1-butene and        polymethyl-1-pentene, ionomers, polyvinyl chloride,        polyvinylidene chloride, polymethyl methacrylate,        polyacrylonitrile, polystyrene, polyacetal, fluoropolymers,        polyvinyl alcohol, polyvinyl acetate and poly-p-xylylene and        also copolymers, such as ethylene-vinyl acetate copolymers,        styrene-acrylonitrile copolymers,        acrylonitrile-butadiene-styrene copolymers, polyethylene glycol        terephthalate and polybutylene glycol terephthalate;    -   polyadducts: thermosets, eg epoxy resin and crosslinked        polyurethanes; thermoplastics, eg linear polyurethanes and        chlorinated polyethers.

Advantageously, plastics are colorable with the pigment preparations ofthe present invention by minimal energy input, for example by conjointextrusion (preferably using a single- or twin-screw extruder), rolling,kneading or grinding. The plastics can be present at that stage asplastically deformable masses or melts and be processed into moldings,film and fiber.

The pigment preparations of the present invention are additionallynotable for altogether advantageous application properties, especiallyfor good color properties, in particular high color strength andbrilliance, and the good rheological properties of the plastics whichhave been colored with them, especially for low pressure-filter values(high filter lifetimes) and good spinnability.

EXAMPLES

Production and Testing of Inventive Pigment Preparations in Granule Form

The pigment preparations were produced by ball milling a suspension of xkg of finished pigment (A), y kg of pigment derivative (B) and z kg ofoptionally plural additives (C) in 150 kg of water, if necessaryadjusted to pH 7 by addition of 25% by weight aqueous sodium hydroxidesolution, to a d₅₀ value <1 μm and then spray granulating the millbasein a spray tower using a one-material nozzle at a gas inlet temperatureof 165° C. and a gas outlet temperature of 70° C.

In examples 39 to 41, pigment (A) was initially coated with the pigmentderivative (B) in an aqueous suspension at pH 8, the coated pigment wasfiltered off and the presscake was then (after prior drying in example41) sent for milling in the presence of additive (C).

The color strength of the pigment granules was determinedcalorimetrically in white reduction (reported in terms of the DIN 55986coloring equivalences) in a waterbome emulsion paint. To this end, amixture of in each case 1.25 g of granular pigment and 50 g of awaterbome styrene/acrylate-based test binder having a white pigmentcontent of 16.4% by weight (TiO₂, Kronos 2043) (BASF test binder00-1067) was homogenized in a 150 ml plastic cup by running a high speedstirrer at 1500 rpm for 3 min. The color obtained was then drawn down ona black and white test card using a 100 μm wire-wound film applicatorand dried for 30 min.

The respective analogous emulsion paints prepared using commerciallyavailable aqueous formulations of the pigments were assigned the CEvalue 100 (standard). CE values <100 denote a higher color strength thanstandard. CE values >100 accordingly denote a lower color strength.

The pigment granules obtained exhibited excellent stability in storage.

The table hereinbelow lists the compositions of the pigment preparationsproduced and also the CE values obtained in each case.

The pigment derivatives (B) used were as follows:

-   -   B1: quinophthalonesulfonic acid (Ia) (WO-A02/00643, example 1)    -   B2: CuPc-sulfonic acid (Ib) having a degree of substitution of        about 1.4    -   B3: CuPc-sulfonic acid (Ib) having a degree of substitution of        about 1.7    -   B4: monolaurylammonium salt of a CuPc-sulfonic acid (Ib) having        a degree of substitution of about 1.4 (similarly to GB-A-1 508        576, agent A)    -   B5: dimethyidistearylammonium salt of a CuPc-sulfonic acid (Ib)        having a degree of substitution of about 1.4 (similarly to        GB-A-1 508 576, agent B)    -   B6: reaction product of a CuPc-sulfonic acid having a degree of        substitution of about 1.7 with 0.6 mol of laurylammonium        chloride    -   B7: perylene-3,4-dicarboximide-9-sulfonic acid (EP-A-636 666,        derivative b2)

The additives (C) used were as follows:

-   -   C1: ethoxylated C₁₃/C₁₅ oxo alcohol having an average degree of        ethoxylation of 30    -   C2: ethoxylated linear saturated C₁₆/C₁₈ fatty alcohol having an        average degree of ethoxylation of 25    -   C3: ethoxylated linear saturated C₁₆/C₁₈ fatty alcohol having an        average degree of ethoxylation of 50    -   C4: block copolymer based on ethylenediamine/propylene        oxide/ethylene oxide, having an ethylene oxide content of 40% by        weight and an average molecular weight M_(n) of 12,000    -   C5: block copolyrner based on ethylenediamine/propylene        oxide/ethylene oxide, having an ethylene oxide content of 40% by        weight and an average molecular weight M_(n) of 6,700    -   C6: ethoxylated saturated isotridecyl alcohol having an average        degree of ethoxylation of 20    -   C7: propylene oxide-ethylene oxide copolymer having a central        propylene oxide block, an ethylene oxide content of 50% by        weight and an average molecular weight M_(n) of 6,500    -   C8: ethoxylated bisphenol A having an average degree of        ethoxylation of 7    -   C9: sodium salt of a monosulfated ethoxylated        tetraphenylethyl-substituted bisphenol A (70 mol EO/mol        bisphenol A) (U.S. Pat. No. 4,218,218, dispersant 13)    -   C10: acidic phosphoric ester based on an initially propoxylated        and then ethoxylated C₈/C₁₀ oxo alcohol (12 mol PO and 6 mol        EO/mol oxo alcohol)

C11: diisobutyinaphthalenesulfonic acid, sodium salt TABLE Pigmentderivative Additives Pigment y z′ z″ z″′ Ex. (A) x kg (B) kg (C) kg (C)kg (C) kg CE 1 P.R. 75.0 B1 2.0 C1 23.0 100 112 2 P.R. 75.0 B1 2.0 C223.0 107 112 3 P.R. 75.0 B1 2.0 C3 23.0 101 112 4 P.R. 78.0 B1 2.0 C410.0 C6 10.0 103 112 5 P.R. 75.0 B1 2.0 C4 23.0 104 112 6 P.R. 75.0 B12.0 C7 23.0 97 112 7 P.R. 74.0 B1 3.0 C7 23.0 99 112 8 P.R. 73.0 B1 2.0C9 25.0 98 112 9 P.R. 73.0 B1 2.0 C6 10.0 C4 15.0 105 112 10 P.R. 76.0B1 4.0 C6 10.0 C4 10.0 101 112 11 P.R. 75.0 B1 2.0 C6 23.0 99 112 12P.R. 77.0 B7 3.0 C4 20.0 102 112 13 P.Y. 73.1 B1 1.5 C1 22.9 C11 2.6 8074 14 P.Y. 76.4 B1 1.6 C1 20.0 C9 2.0 98 74 15 P.Y. 73.5 B1 1.5 C2 25.098 74 16 P.Y. 75.9 B1 1.6 C2 19.9 C11 2.6 95 74 17 P.Y. 72.8 B1 2.3 C224.0 C11 1.0 90 74 18 P.Y. 73.5 B1 1.5 C3 25.0 105 74 19 P.Y. 74.5 B11.5 C3 23.0 C11 1.0 93 74 20 P.Y. 77.2 B1 0.8 C4 19.5 C11 2.5 88 74 21P.Y. 78.4 B1 1.6 C4 10.0 C1 10.0 102 74 22 P.Y. 78.4 B1 1.6 C4 10.0 C610.0 102 74 23 P.Y. 78.4 B1 1.6 C7 10.0 C1 5.0 C6 5.0 105 74 24 P.V.73.5 B3 1.5 C4 25.0 103 23 25 P.V. 73.5 B3 1.5 C8 25.0 98 23 26 P.Y.82.5 B1 0.5 C7 17.0 92 138 27 P.Y. 79.0 B1 1.0 C7 5.0 C10 15.0 101 13828 P.Y. 79.0 B1 1.0 C7 15.0 C10 5.0 91 138 29 P.B. 75.1 B4 4.9 C4 20.093 15 30 P.B. 75.0 B4 5.0 C2 20.0 101 15:1 31 P.B. 75.0 B4 5.0 C4 20.097 15:1 32 P.B. 73.1 B4 3.9 C4 23.0 106 15:1 33 P.B. 76.0 B3 4.0 C4 20.0104 15:1 34 P.B. 76.0 B2 4.0 C4 20.0 105 15:1 35 P.B. 72.1 B5 5.4 C422.5 100 15:1 36 P.B. 72.7 B2 4.5 C4 22.7 102 15:2 37 P.B. 70.3 B4 4.7C4 25.0 102 15:2 38 P.B. 75.0 B4 5.0 C4 20.0 93 15:2 39 P.B. 75.0 B6 5.0C4 20.0 102 15:2 40 P.B. 75.0 B3 5.0 C4 19.9 98 15:2 41 P.B. 75.0 B3 5.0C4 20.0 98 15:2 42 P.O. 76.0 B1 2.0 C4 22.0 88 67 43 P.O. 76.0 B1 2.0 C522.0 93 67 44 P.O. 75.0 B1 3.0 C5 22.0 93 67 45 P.O. 75.0 B1 3.0 C3 22.091 67 46 P.O. 76.0 B1 2.0 C8 22.0 84 67

1: A solid pigment preparation comprising (A) from 60% to 85% by weightof at least one organic pigment, (B) from 0.1% to 15% by weight of atleast one pigment derivative of the general formula I

where P is the residue of the core structure of an organic pigmentselected from the group consisting of quinophthalone and phthalocyaninepigments; T¹ and T² are independently a chemical bond, —CONR¹ — or—SO₂NR¹—; B¹ and B² are independently a chemical bond, C₁-C₈-alkylene orphenylene; X and Y independently represent identical or different groups—SO₃ ⁻Ka⁺ or —COO⁻Ka⁺; m and n are each a rational number from 0 to 3subject to the proviso that 1≦m+n≦4; Ka⁺ is H⁺, Li⁺, Na⁺, K⁺, N⁺R²R³R⁴R⁵or a mixture thereof; R¹ is hydrogen; C₁-C₄-alkyl; unsubstituted orC₁-C₁₈-alkyl-substituted phenyl; or unsubstituted orC₁-C₁₈alkyl-substituted naphthyl; R², R³, R⁴ and R⁵ are independentlyhydrogen; C₁-C₃₀-alkyl; C₃-C₃₀-alkenyl; C₅-C₆-cycloalkyl, unsubstitutedor C₁-C₂₄-alkyl-substituted; unsubstituted or C₁-C₂₄-alkyl— orC₂-C₂₄-alkenyl-substituted phenyl; unsubstituted or C₁-C₂₄-alkyl— orC₂-C₂₄-alkenyl-substituted naphthyl; a radical of the formula−[CHR⁶—CHR⁷—O]_(x)—R⁸ where the repeat units −[CHR⁶—CHR⁷—O] can vary forx>1; R⁶, R⁷and R⁸ are independently hydrogen or C₁-C₆-alkyl; x is aninteger ≧1, and (C) from 14.9% by weight to 39.9% by weight of at leastone surface-active additive selected from the group consisting of thenonionic polyethers comprising no primary amino group, said polyethers'acidic phosphoric, phosphonic, sulfuric and/or sulfonic esters, thesalts of these esters and the alkyl- and alkylarylsulfonic acids, theirsalts and their condensation products with formaldehyde. 2: The solidpigment preparation as claimed in claim 1 in the form of granules havingan average particle size from 50 to 5,000 μm and a BET surface area of≦15 m²/g. 3: The solid pigment preparation as claimed in claim 1,wherein component (C) is at least one additive selected from the groupconsisting of the alkylene oxide copolymers, the reaction products ofalkylene oxides with alcohols, amines, aliphatic carboxylic acids orcarboxamides, the acidic phosphoric, phosphonic, sulfuric and sulfonicesters of these alkylene oxide compounds, the salts of these esters andthe alkylphenyl- and alkylnaphthalenesulfonic acids, their salts andtheir condensation products with formaldehyde. 4: A process forproducing pigment preparations as claimed in claim 1, comprisingwet-comminuting the pigment (A) in aqueous suspension which comprisessome or all of additive (C) and, optionally, some or all of pigmentderivative (B) and also, optionally, prior or subsequent neutralizationof the suspension with a base and then drying the suspension, ifnecessary after the rest of pigment derivative (B) and additive (C) hasbeen added. 5: A process for coloration of macromolecular organic andinorganic materials, comprising incorporating pigment preparations asclaimed in claim 1 in these materials by stirring or shaking. 6: Theprocess as claimed in claim 5 for coloration of coatings, paints, inks,including printing inks, and finish systems where the liquid phasecomprises water, organic solvents or mixtures of water and organicsolvents. 7: A process for coloration of macromolecular organic andinorganic materials with color-mixing systems, comprising utilizingpigment preparations as claimed in claim 1 as mixing components. 8: Aprocess for coloration of plastics, comprising incorporating pigmentpreparations as claimed in claim 1 in the plastics by extruding,rolling, kneading or milling.